Novel photoresponsive nano scrolls of tantalotungstate intercalated with C 3 F 7 -Azo + were synthesized by guest−guest ion exchange. Physicochemical characterization utilizing X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) verified the successful synthesis of spiral nano scrolls. XRD and UV data evidenced aggregated conformations of C 3 F 7 -Azo + with end-to-end J-type configurations between the tantalum tungstate layers. The nano scrolls exhibited reversible trans−cis photoisomerization under ultraviolet and visible light irradiation at 365 and 440 nm, respectively, while the basal spacing accompanying the photoresponse was reversibly changed. Overall, photofunctional tantalum tungstate nano scrolls have promising applications in optoelectronic devices.